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EP3793985B1 - Verfahren zur herstellung von dioxolan - Google Patents

Verfahren zur herstellung von dioxolan Download PDF

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Publication number
EP3793985B1
EP3793985B1 EP19720019.9A EP19720019A EP3793985B1 EP 3793985 B1 EP3793985 B1 EP 3793985B1 EP 19720019 A EP19720019 A EP 19720019A EP 3793985 B1 EP3793985 B1 EP 3793985B1
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EP
European Patent Office
Prior art keywords
stream
separation unit
column
phase separation
dioxolane
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EP19720019.9A
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English (en)
French (fr)
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EP3793985A1 (de
Inventor
Thomas Heitz
Marvin KRAMP
Manfred Heilig
HyunSoo CHANG
Jongmoon Kim
In Gi Cho
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BASF SE
Kolon ENP Inc
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BASF SE
Kolon Plastics Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to a process for preparing dioxolane by reacting ethylene glycol with an aqueous solution of formaldehyde in the presence of an acid catalyst.
  • 1,3-dioxacyclopentane is a derivative of ethylene glycol which is used industrially and can be prepared by reacting ethylene glycol with an aqueous formaldehyde solution in the presence of acid catalysts such as sulfuric acid, boron trifluoride, zinc chloride or acid ion exchangers. Pure dioxolane can be isolated from the reaction mixture using various separation methods, in particular by distillation or extraction.
  • WO 2012/177598 A1 discloses a process for the production of cyclic acetals in a reactive distillation column by combining a polyhydroxyl compound and an aldehyde. High concentrations of cyclic acetals are removed as liquid products from the column while water is removed as an overhead vapor stream.
  • US patent 5,695,615 discloses a purification process for cyclic formals, in which water is removed from a crude cyclic formal by supplying a hydrophilic solvent to the mixture, thereby obtaining a cyclic formal of high purity which contains only a small amount of water.
  • the document CN 1149055 A discloses a process similar to that of the previous document but using alkyl-substituted benzenes like toluene to break the azeotrope of dioxolane and water. Even though the proposed process yields dioxolane in high purity, the process is characterized by a large capital investment as at least four distillation columns are necessary and a significant portion of the desired product dioxolane is lost in the step of dewatering the reaction mixture.
  • the German patent application DE 10 2005 042 505 A1 discloses a process for preparing dioxolane by reacting ethylene glycol with formaldehyde in aqueous solution in the presence of catalysts, wherein the reaction is carried out in a reactive distillation column.
  • the azeotropic mixture of mainly dioxolane and water is withdrawn from the top of the column and fed to a further distillation column which is operated at an elevated pressure to obtain purified dioxolane as the bottom product.
  • the bottom stream of the reaction column is fed to a further distillation column to separate off the water and to recycle unreacted ethylene glycol. Even though this process does not need any extracting agent like benzene in the previous process, part of the dioxolane produced is lost due to a necessary discharge from the top of the dioxolane purification column.
  • the process for preparing dioxolane comprises the following steps:
  • the inventive process is a continuous process, such that the above-mentioned steps (a) to (d) are performed simultaneously.
  • the reaction distillation device used in step (a) can be any combination of reaction and distillation that enables the reaction of ethylene glycol and formaldehyde to obtain dioxolane.
  • the reaction distillation device is set up as a reactor that is directly coupled with a distillation column.
  • the reaction distillation device is set up as a reactive distillation column where the catalyst is embedded on trays or stages of the distillation column, preferably in the lower part of the distillation column.
  • the reaction distillation device is set up as a reactor directly coupled to a reactive distillation column where catalyst is present in the reactor as well as in a part of the distillation column.
  • the mass fraction of methanol in the distillate stream from the reaction distillation device is from 0.02 % to 5 % by weight.
  • the mass fraction of methanol in the bottom product stream of the purification column is less than 0.5 %, more preferably less than 0.1 %, most preferably less than 0.05 %, in particular less than 0.01 %.
  • Methanol is usually present in small amounts in the feed stream of the aqueous formaldehyde, mainly due to an incomplete conversion of methanol in the formaldehyde production process. Furthermore, methanol acts as a stabilizer for the formalin solution. Despite the small amounts present in the feed stream, it has been found that due to the full recycle of the water methanol accumulates and leads to maloperations in the long run. This problem is not discussed in the prior art at all. The inventive solution of withdrawing a distillate stream containing methanol from the waste water column solves this problem.
  • an additional side stream containing methanol is withdrawn from a stage below the feed stage of the waste water column.
  • methanol accumulates in the middle region of the column.
  • the additional side stream withdrawal can be advantageous for the removal of methanol and thus the stable operation of the process.
  • an additional water containing stream is fed to the phase separation unit.
  • Water is transferred to the phase separation unit in step (b) of the process according to the invention as it is one component of the distillate stream of the reaction distillation device. The largest part of that water is transferred in the aqueous phase from the phase separation unit to the waste water column.
  • adding additional water increases the range of operability of the phase separation unit and therefore has an advantageous effect on a stable operation of the inventive process.
  • composition of the organic extracting agent there is no specific restriction with respect to the composition of the organic extracting agent, provided that it is able to separate dioxolane and water.
  • organic extracting agent is selected from the group of substances that fulfill the following conditions:
  • Condition (a) ensures that there exists a miscibility gap in the phase separation unit, which enhances the separation of the organic phase from the aqueous phase.
  • Condition (b) ensures the enrichment of methanol in the aqueous fraction stream leaving the phase separation unit.
  • Conditions (c) guarantee that there are no heavy boiling azeotropes present which would hinder the separation into pure components.
  • Conditions (d) depend on the vapor pressures of the pure components and facilitate an azeotropic distillation. For conditions (d) all pure component vapor pressures are calculated at a temperature of 334.85 K.
  • the pure component vapor pressure data can be derived from a vapor pressure function of experimental data and limiting activity coefficients (activity coefficients at infinite dilution) can be calculated by the quantumchemical continuum solvation model Cosmo-RS (COSMOthermX Version C30_1702, developed and copyright by COSMOlogic GmbH&Co.KG, Imbacher Weg 46, 51379 Leverkusen, Germany) with the parameterization BP_TZVP_C30_1701.
  • Cosmo-RS COSMOthermX Version C30_1702, developed and copyright by COSMOlogic GmbH&Co.KG, Imbacher Weg 46, 51379 Leverkusen, Germany
  • the extracting agent is selected from the group consisting of pentane, cyclopentane, 2,2-dimethylbutane, 2,3-dimethylbutane, methylisobutylether, 2-methylpentane, 3-methylpentane, propylisopropylether, hexane, methylcyclopentane, 2,2-dimethylpentane, 2,4-dimethylpentane, cyclohexane, 3,3-dimethylpentane, 2-ethyl-3-methyl-1-butene, 1,1-dimethylcyclopentane, 2-methylhexane, di-n-propylether, (z)-1,3-dimethylcyclopentane, trans-1,2-dimethylcyclopentane, trans-1,3-dimethylcyclopentane, 3-methyl-hexane, 1-ethoxybutane, 3-ethylpentane, 2,2,4-trimethylpentane
  • Table 1 shows the values for the pure component vapor pressure and the limiting activity coefficients calculated with the above-mentioned Cosmo-RS model.
  • Table 1 CAS Extracting Agent P 0 EA (hPa) gamma _inf_29 8 (methanol in water) gamma _ inf _298 (EA in water) gamma_in f_298 (water in EA) gamma_i nf_298 (methanol in EA) gamma_i nf_335 (EA in dioxolane) i - gamma_inf _335 (EA in water) gamma _inf 33 5 (dioxolane in EA) gamma_i nf_335 (water in EA) 109-66-0 pentane 2976.4 2.08 37456.79 1736.05 252.56 4.20 20026.37 4.22 216.88 287-92-3 cyclopentane 2010.0 2.
  • the extracting agent is selected from the group consisting of isomers of hexane (C 6 H 14 ). Isomers of hexane are n-hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane and 2,2-dimethylbutane.
  • the extracting agent may comprise a single isomer or a mixture of isomers of hexane. Further substances can be present in the extracting agent, for example other C 6 hydrocarbons like cyclohexane or methylcyclopentane (C 6 H 12 ).
  • the extracting agent comprises n-hexane with a mass fraction of at least 80 %, preferably at least 90 %, more preferably at least 95 %, in particular at least 99 %.
  • Particularly preferred technically pure grades of hexane typically contain 99 % or more of n-hexane and amounts of up to 1 % in total of various C 6 isomers, including cyclohexane and methylcyclopentane.
  • a high purity of n-hexane is preferred to avoid an accumulation of side component in the extracting agent.
  • a make-up stream containing the organic extracting agent is fed to the phase separation unit.
  • One advantage of the process according to the invention over the prior art is the full recycle of the extracting agent by design and consequently no loss of extracting agent.
  • the extracting agent has to be provided at the startup of the process once. Afterwards, the extracting agent stays in the process. However, due to operational disturbances or malfunctions, it might happen that extracting agent is withdrawn from the process in an outgoing stream.
  • the provision of a make-up stream of extracting agent is advantageous for a stable operation of the process.
  • the make-up stream can be fed to any process stream or process unit.
  • the make-up stream is fed to the phase separation unit. More preferably, the make-up stream is fed to a mixing device of the phase separation unit.
  • the phase separation unit comprises a mixer and a phase separator.
  • the distillate stream from the reaction distillation device, the distillate stream from the purification column, the side stream from the waste water column and optionally the additional water containing stream and/or the make-up stream containing the organic extracting agent are fed to and mixed in the mixer.
  • the outlet stream of the mixer is fed to the phase separator.
  • Mixing the streams in a first step and separating the phases in a second step has the advantage that the mixture fed to the phase separator is more homogeneous, e.g. in terms of droplet size, compared to feeding the streams directly into the phase separator without mixing step.
  • the mixer can be any kind of mixing device that provides a thorough and homogeneous mixture.
  • the mixer is a static mixer.
  • the mixed stream in the outlet of the mixer is fed to a cooling device where the temperature of the mixed stream is reduced before it is fed to the phase separator. Reducing the temperature of the mixed stream facilitates a stable operation of the phase separation.
  • Dioxolane is produced and provided in a very high purity without significant loss of product via other streams. Side components, especially methanol, is efficiently removed. The extracting agent used is recycled without material loss.
  • the process can be operated in a stable and reliable manner on an industrial and commercial scale.
  • Fig. 1 shows a block diagram of a first embodiment of the process according to the invention.
  • the block diagram only shows the main operation units.
  • Auxiliary equipment like reboilers, condensers, pumps, valves and instrumentation equipment is not depicted in Fig. 1 .
  • a feed stream 1 containing ethylene glycol and a feed stream 2 containing formaldehyde and methanol in an aqueous solution are fed into the lower region of a reaction distillation device 10.
  • At least one catalyst is present in the reaction distillation device 10, preferably in the lower part of the device.
  • the catalyst enables the reaction of ethylene glycol and formaldehyde in aqueous solution to form a raw reaction product which comprises water, dioxolane and methanol.
  • the raw product is withdrawn from the top of the reaction distillation device 10, part of it is condensed and recycled as reflux to the reaction distillation device 10 (not shown), and the remainder is transferred as distillate stream 11 to a phase separation unit 20.
  • an organic extracting agent is present that enhances the separation of the inflowing substances into an aqueous fraction and an organic fraction.
  • the organic fraction is withdrawn from the phase separation unit 20 in stream 21 and is transferred to an upper part of a purification column 30.
  • the aqueous fraction is withdrawn from the phase separation unit 20 in stream 22 and is transferred to a waste water column 40.
  • the purification column 30 is equipped with a reboiler (not shown) that evaporates parts of the material present in the bottom part of the column such that there is a counter flow regime of the organic material fed in stream 21 and the vapor produced in the reboiler inside the column.
  • the remaining part of the material in the bottom of the purification column 30 is withdrawn as bottom product stream 31 which is rich in dioxolane.
  • the up-flowing material is withdrawn as a distillate stream 32 from the purification column 30 and is recycled to the phase separation unit 20.
  • the aqueous fraction stream 22 from the phase separation unit 20 is fed to a middle section of the waste water column 40.
  • the column is equipped with a reboiler and a condenser (not shown) that enable a counter flow regime of liquid and vapor in the column.
  • Part of the liquid material in the bottom of the column is withdrawn as a water rich waste water stream 41.
  • the remainder is fed to the reboiler.
  • the overhead stream leaving the top of the waste water column 40 is fed to the condenser.
  • the main part of the condensed material is recycled as reflux to the column.
  • the remainder is withdrawn as a distillate stream 43 containing methanol.
  • a side stream 42 is withdrawn from a stage between the feed stage and the reflux stage of the waste water column 40 and is recycled to the phase separation unit 20.
  • an additional water containing stream 23 and/or a make-up stream 24 containing the organic extracting agent is fed to the phase separation unit 20.
  • Fig. 2 shows a block diagram of a second embodiment of the process according to the invention.
  • This process is a modification of the first embodiment shown in Fig. 1 .
  • the main difference is an additional side stream 44 containing methanol which is withdrawn from a stage below the feed stage of the waste water column 40.
  • the additional side stream 44 contains methanol but merely no dioxolane.
  • the methanol load of the upper part of the waste water column 40 is reduced which allows to reduce the distillate stream 43 compared to the first embodiment shown in Fig. 1 .
  • Fig. 3 shows a preferred embodiment of a phase separation unit 20 according to the invention.
  • the phase separation unit 20 comprises a mixer 25 and a phase separator 26.
  • the distillate stream 11 from the reaction distillation device, the distillate stream 32 from the purification column and the side stream 42 from the waste water column are fed to the mixer 25.
  • the additional water containing stream 23 and/or the make-up stream 24 containing the organic extracting agent are fed to the mixer 25 as well. All streams are mixed in the mixer 25, the outlet stream of the mixer is fed to a cooling device 27 where the temperature of the mixed stream is reduced, and the outlet stream of the cooling device 27 is fed to the phase separator 26.
  • the reaction distillation device 10 was set up as a reactor directly coupled to a distillation column with 30 trays. 145 kg/h of an aqueous solution containing 65 wt% of formaldehyde and 0.6 wt% of methanol were continuously fed to the reactor. 185 kg/h ethylene glycol were continuously fed to the 10th tray (counting from the top) of the distillation column and was in counter-current flow to the dioxolane raw product flowing out of the reactor. Sulfuric acid was used as catalyst, its concentration being 2 wt% with respect to the reactor content.
  • a distillate stream 11 containing the raw product was transferred from the top of the reaction distillation device 10 to a phase separation unit 20.
  • the phase separation unit comprised a static mixer 25 and a phase separator 26.
  • An additional water stream 23 was fed to the mixer at a feed rate of 205 kg/h.
  • n-Hexane had been filled into the plant during start-up as an organic extracting agent.
  • the mass fraction of n-hexane in the organic extracting agent was 99 % with isomers of n-hexane (C 6 H 14 ) and C 6 H 12 components summing up to the remaining 1 %.
  • the n-hexane used fulfills the following criteria:
  • An organic fraction stream 21 was transferred from the phase separation unit 20 to the uppermost tray of the purification column 30.
  • the distillate stream 32 was recycled to the mixer 25 of the phase separation unit 20.
  • From the bottom of the column dioxolane with a purity of 99.9 wt% was withdrawn as a bottom product stream 31 at a rate of 190 kg/h.
  • the water content in the dioxolane product was 43 ppm.
  • the methanol content was 69 ppm. No extracting agent (n-hexane) was detected in the dioxolane product.
  • a stream 22 containing the aqueous fraction of the phase separator was transferred to the 20th tray (counting from top with 30 trays in total) of the waste water column 40.
  • a waste water stream 41 was withdrawn from the bottom of that column with a water content of 98.3 wt%. Non-reacted formaldehyde (1.6 wt%) was also discharged with the waste water stream 41.
  • a side stream 42 was withdrawn from tray 10 of the waste water column and recycled to the mixer 25.
  • the distillate stream 43 from the waste water column was condensed and partially recycled to the top of the column as a reflux stream.
  • the remaining portion of the distillate stream 43 was withdrawn from the waste water column at a rate of 28.5 kg/h.
  • This stream contained 85.5 wt% dioxolane, 9.1 wt% water, 0.9 wt% methanol as well as minor amounts of formaldehyde and n-hexane.
  • Example 4 of the document EP 0 867 434 A1 is compared with Example 4 of the document EP 0 867 434 A1 .
  • the main differences are the column configuration in terms of column sequence and the lack of a phase separation unit in the prior art, as well as in the selection of the extracting agent.
  • dewatering column water is withdrawn from the bottom and a distillate stream at a rate of 136 g/h of an azeotropic mixture containing 91.8 wt% dioxolane and 7.6 wt% water is withdrawn and fed to a purification column.
  • benzene is added as an extracting agent at a flow rate of 16 g/h to the purification column.
  • Dioxolane is obtained as a bottom product from the purification column at a flow rate of 135 g/h with a benzene concentration of 11 wt% in the dioxolane product stream.
  • the water content was 44 ppm.
  • the process according to the invention provides a significantly higher purity of the desired dioxolane product.
  • the extracting agent is nearly completely used in internal recycles. An expensive treatment or processing of the extracting agent is not necessary in the inventive process - in contrast to the process of the prior art.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Claims (10)

  1. Verfahren zur Herstellung von Dioxolan, das folgende Schritte umfasst:
    a) Einspeisen eines ersten Zulaufstroms (1), der Ethylenglykol enthält, und eines zweiten Zulaufstroms (2), der Formaldehyd und Methanol in wässriger Lösung enthält, in eine Reaktivdestillationsvorrichtung (10) und Umsetzen von Ethylenglykol und Formaldehyd in wässriger Lösung in Gegenwart von mindestens einem Katalysator unter Erhalt eines Rohprodukts, das Wasser, Dioxolan und Methanol umfasst,
    b) Überführen eines Destillatstroms (11), der Rohprodukt enthält, vom Kopf der Reaktivdestillationsvorrichtung (10) zu einer Phasentrenneinheit (20), wobei in der Phasentrenneinheit (20) ein organisches Extraktionsmittel vorliegt,
    c) Überführen eines Stroms (21) einer organischen Fraktion aus der Phasentrenneinheit (20) zu einem oberen Teil einer Reinigungskolonne (30), Abziehen eines Sumpfproduktstroms (31), der Dioxolan enthält, aus der Reinigungskolonne (30) und Zurückführen eines Destillatstroms (32) von der Reinigungskolonne (30) zur Phasentrenneinheit (20),
    d) Überführen eines Stroms (22) einer wässrigen Fraktion aus der Phasentrenneinheit (20) zu einer Abwasserkolonne (40), Abziehen eines Abwasserstroms (41) aus dem Sumpf der Abwasserkolonne (40), Abziehen eines Seitenstroms (42) aus einer Stufe zwischen der Zufuhrstufe und der Rückflussstufe der Abwassersäule (40) und Zurückführen dieses Stroms (42) zur Phasentrenneinheit (20) und Abziehen eines Destillatstroms (43), der Methanol enthält, aus der Abwasserkolonne (40).
  2. Verfahren nach Anspruch 1, wobei ein Seitenstrom (44), der Methanol enthält, aus einer Stufe unterhalb der Zufuhrstufe der Abwasserkolonne (40) abgezogen wird.
  3. Verfahren nach Anspruch 1 oder 2, wobei ein zusätzlicher wasserhaltiger Strom (23) in die Phasentrenneinheit (20) eingespeist wird.
  4. Verfahren nach einem der Ansprüche 1 bis 3, wobei das Extraktionsmittel aus der Gruppe bestehend aus Pentan, Cyclopentan, 2,2-Dimethylbutan, 2,3-Dimethylbutan, Methylisobutylether, 2-Methylpentan, 3-Methylpentan, Propylisopropylether, Hexan, Methylcyclopentan, 2,2-Dimethylpentan, 2,4-Dimethylpentan, Cyclohexan, 3,3-Dimethylpentan, 2-Ethyl-3-methyl-1-buten, 1,1-Dimethylcyclopentan, 2-Methylhexan, Di-n-propylether, (z)-1,3-Dimethylcyclopentan, trans-1,2-Dimethylcyclopentan, trans-1,3-Dimethylcyclopentan, 3-Methylhexan, 1-Ethoxybutan, 3-Ethylpentan, 2,2,4-Trimethylpentan, n-Heptan, Isopropylisobutylether, (z)-1,2-Dimethylcyclopentan, 2,2-Dimethylhexan, 2,3-Dimethylhexan, 2,4-Dimethylhexan, 2,5-Dimethylhexan, 3,4-Dimethylhexan, 2-Methylheptan und Octan ausgewählt ist.
  5. Verfahren nach einem der Ansprüche 1 bis 3, wobei das Extraktionsmittel aus der Gruppe bestehend aus Isomeren von Hexan (C6H14) ausgewählt ist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, wobei das Extraktionsmittel n-Hexan mit einem Massenanteil von mindestens 80 %, bevorzugt mindestens 90 %, weiter bevorzugt mindestens 95 %, insbesondere mindestens 99 %, umfasst.
  7. Verfahren nach einem der Ansprüche 1 bis 6, wobei ein Make-up-Strom (24), der das organische Extraktionsmittel enthält, in die Phasentrenneinheit (20) eingespeist wird.
  8. Verfahren nach einem der Ansprüche 1 bis 7, wobei die Phasentrenneinheit (20) einen Mischer (25) und einen Phasenscheider (26) umfasst, wobei der Destillatstrom (11) aus der Reaktivdestillationsvorrichtung (10), der Destillatstrom (32) aus der Reinigungskolonne (30), der Seitenstrom (42) aus der Abwasserkolonne (40) und gegebenenfalls der zusätzliche wasserhaltige Strom (23) und/oder der Make-up-Strom (24), der das organische Extraktionsmittel enthält, in den Mischer (25) eingespeist und darin gemischt werden und der Auslassstrom des Mischers (25) in den Phasenscheider (26) eingespeist wird.
  9. Verfahren nach einem der Ansprüche 1 bis 8, wobei der Massenanteil an Methanol im Destillatstrom (11) aus der Reaktivdestillationsvorrichtung (10) 0,02 % bis 5 % beträgt.
  10. Verfahren nach einem der Ansprüche 1 bis 9, wobei der Massenanteil an Methanol im Sumpfproduktstrom (31) der Reinigungskolonne (30) weniger als 0,5 %, bevorzugt weniger als 0,1 %, weiter bevorzugt weniger als 0,05 %, insbesondere weniger als 0,01 %, beträgt.
EP19720019.9A 2018-05-18 2019-05-08 Verfahren zur herstellung von dioxolan Active EP3793985B1 (de)

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EP18173076 2018-05-18
PCT/EP2019/061773 WO2019219468A1 (en) 2018-05-18 2019-05-08 Process for preparing dioxolane

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EP3793985B1 true EP3793985B1 (de) 2022-10-12

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EP (1) EP3793985B1 (de)
JP (1) JP7337149B2 (de)
KR (1) KR102906819B1 (de)
CN (1) CN112292371B (de)
MY (1) MY206328A (de)
PL (1) PL3793985T3 (de)
WO (1) WO2019219468A1 (de)

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CN112292372B (zh) 2018-05-18 2024-10-15 巴斯夫欧洲公司 制备二氧戊环的方法
CN111978284A (zh) * 2020-08-14 2020-11-24 中化学科学技术研究有限公司 一种二氧五环制备工艺及制备系统
CN116947803B (zh) * 2023-06-20 2025-11-21 中国五环工程有限公司 二氧五环生产方法

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MY206328A (en) 2024-12-11
WO2019219468A1 (en) 2019-11-21
KR102906819B1 (ko) 2025-12-31
PL3793985T3 (pl) 2023-02-13
JP7337149B2 (ja) 2023-09-01
US11655228B2 (en) 2023-05-23
CN112292371A (zh) 2021-01-29
JP2021524502A (ja) 2021-09-13
EP3793985A1 (de) 2021-03-24
KR20210013131A (ko) 2021-02-03

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